Semiconductor devices including an epitaxial layer with a slanted surface

ABSTRACT

A method of fabricating one or more semiconductor devices includes forming a trench in a semiconductor substrate, performing a cycling process to remove contaminants from the trench, and forming an epitaxial layer on the trench. The cycling process includes sequentially supplying a first reaction gas containing germane, hydrogen chloride and hydrogen and a second reaction gas containing hydrogen chloride and hydrogen onto the semiconductor substrate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This U.S. non-provisional patent application is a ContinuationApplication of prior application Ser. No. 13/422,077, filed on Mar. 16,2012 in the United States Patent and Trademark Office, which claimspriority under 35 U.S.C. §119(a) from Korean Patent Application No.10-2011-0026052, filed on Mar. 23, 2011, in the Korean IntellectualProperty Office, the entire contents of which are hereby incorporated byreference.

BACKGROUND

1. Field of the General Inventive Concept

The general inventive concept relates to a semiconductor device. Moreparticularly, the general inventive concept relates to a method offabricating a semiconductor device having an improved performance.

2. Description of the Related Art

There has been intensive research to increase an integration density ofa semiconductor device and improve performance thereof, such as anoperating speed and an operating electric current. For instance, inorder to improve the performance of the semiconductor device, there havebeen suggested methods of inducing strain or stress to a transistor.

SUMMARY

The present general inventive concept provides fabrication methodscapable of effectively applying strain or stress to a transistor channelof a semiconductor device, thereby increasing carrier mobility.

Additional features and utilities of the present general inventiveconcept will be set forth in part in the description which follows and,in part, will be obvious from the description, or may be learned bypractice of the general inventive concept.

Other exemplary embodiments of the present general inventive conceptprovide methods of fabricating a semiconductor device with a highquality epitaxial layer.

Still other exemplary embodiments of the present general inventiveconcept provide semiconductor device fabrication methods capable ofsharply maintaining a profile of a trench and effectively removing anative oxide layer and/or a contaminant.

According to some features of the present general inventive concept, anative oxide layer can be removed from a trench surface using a reactiongas containing germanium, and an extra germanium layer, which may beunintentionally deposited on the trench surface, can be removed using asecond reaction gas capable of etching germanium. According to otherfeatures of the present general inventive concept, the trench can bemaintained to have a sharp tip. According to still other features of thepresent general inventive concept, it is possible to maintain the tip ofthe trench sharply. Further, it may be possible to suppress and/orprevent the trench from being deformed. According to even other featuresof the present general inventive concept, it is possible to effectivelyremove elements or factors providing a negative effect on a growth rateof an epitaxial layer in at least one exemplary embodiment, a seed layerto grow an epitaxial layer can be prepared to have a clean surface,before growing the epitaxial layer.

According to exemplary embodiments of the present general inventiveconcept, a method of fabricating a semiconductor device may includeforming a trench in a semiconductor substrate, performing a cyclingprocess to remove contaminants from the trench, the cycling processincluding sequentially supplying a first reaction gas and a secondreaction gas onto the semiconductor substrate, the first reaction gascontaining germane (GeH4), hydrogen chloride (HCl) and hydrogen (H2) andthe second reaction gas containing hydrogen chloride (HCl) and hydrogen(H2), and forming an epitaxial layer on the trench.

In at least one exemplary embodiment, the performing of the cyclingprocess may include removing a native oxide layer from the trench usingthe germane (GeH4) of the first reaction gas and removing a germaniumlayer from the trench using the hydrogen chloride (HCl) of the firstreaction gas.

In at least one exemplary embodiment, the performing of the cyclingprocess may further include removing a remaining portion of thegermanium layer, which may not be removed by the first reaction gas,using the hydrogen chloride (HCl) of the second reaction gas.

In at least one exemplary embodiment, the supplying of the firstreaction gas may include supplying the first reaction gas under apressure of about 1 Torr to about 100 Torr at a temperature of about500° C. to about 800° C.

In at least one exemplary embodiment, the supplying of the firstreaction gas may include supplying the hydrogen chloride (HCl) with aflow rate greater than 150 times a flow rate of the germane (GeH4).

In at least one exemplary embodiment, the supplying of the firstreaction gas may include supplying the germane (GeH4) with a partialpressure of 0.3 mTorr or less and with a flow rate of about 0.75 sccm ormore.

In at least one exemplary embodiment, the supplying of the firstreaction gas may include supplying the hydrogen chloride (HCl) with apartial pressure greater than 150 times a partial pressure of thegermane (GeH4) and with a flow rate of about 150 sccm or more.

In at least one exemplary embodiment, at least one of the supplying ofthe first reaction gas and the supplying of the second reaction gas mayinclude the hydrogen (H2) with a flow rate of about 30 slm to about 50slm.

In at least one exemplary embodiment, the supplying of the secondreaction gas may include supplying the second reaction gas under apressure of about 1 Torr to about 100 Torr at a temperature of about500° C. to about 800° C. or about 700° C. to about 800° C. during aprocess time, of which a temporal length ratio relative to the firstreaction gas may be about 0.1 to about 10.

In at least one exemplary embodiment, the performing of the cyclingprocess may include sequentially supplying the first reaction gas andthe second reaction gas, under a pressure of about 1 Torr to about 100Torr at a temperature of about 500° C. to about 800° C.

In at least one exemplary embodiment, the forming of the epitaxial layermay include growing a layer with a different lattice constant from thesemiconductor substrate from a surface of the trench.

According to other exemplary embodiments of the present generalinventive concept, a method of fabricating a semiconductor device mayinclude forming a plurality of gate electrode structures on asemiconductor substrate, etching the semiconductor substrate between thegate electrode structures to form a trench including inner surfacesdefining at least one tip, some of the inner surfaces having arelatively high density compared with the others of the inner surfaces,and the tip protruding toward a channel region, which may be a portionof the semiconductor substrate below the gate electrode structure,supplying a first reaction gas containing germane (GeH4), hydrogenchloride (HCl) and hydrogen (H2) onto the semiconductor substrate toremove a native oxide layer and a germanium layer from the innersurfaces of the trench, supplying a second reaction gas containinghydrogen chloride (HCl) and hydrogen (H2) onto the semiconductorsubstrate to remove a remaining portion of the germanium layer, whichmay not be removed by the first reaction gas, and forming a junctionregion in the trench.

In at least one exemplary embodiment, the semiconductor substrate may bea silicon substrate having a top surface of (100) crystal plane, and theforming of the trench may include forming inner surfaces having a (111)crystal plane, which serve as the inner surfaces having a relativelyhigh density. The tip may be provided as a corner defined by the innersurfaces of the (111) crystal plane.

In at least one exemplary embodiment, the forming of the trench mayinclude isotropically etching the semiconductor substrate using a dryetching process to form a preliminary trench having a substantiallyelliptical profile in the semiconductor substrate, and etching thesemiconductor substrate using a wet etching process to enlarge thepreliminary trench. The trench may be formed to have a sigma (Σ) shapedprofile defined by the inner surfaces of the (111) crystal plane.

In at least one exemplary embodiment, the forming of the junction regionmay include epitaxially growing a layer with a different latticeconstant from the semiconductor substrate.

In at least one exemplary embodiment, the forming of the junction regionmay include epitaxially growing a silicon-germanium (SiGe) layer with alattice constant greater than the semiconductor substrate of silicon,and the gate electrode structure and the junction region constitute aPMOS transistor.

In at least one exemplary embodiment, the forming of the junction regionmay include epitaxially growing a silicon-carbide (SiC) layer with alattice constant smaller than the semiconductor substrate of silicon,and the gate electrode structure and the junction region constitute anNMOS transistor.

In at least one exemplary embodiment, the supplying of the firstreaction gas may be followed by the supplying of the second reactiongas, and the method may include performing the sequential supplying ofthe first and second reaction gases onto the semiconductor substrate oneor more times.

In at least one exemplary embodiment, at least one of the supplying ofthe first reaction gas and the supplying of the second reaction gas maybe performed under a pressure of about 1 Torr to about 100 Torr at atemperature of about 500° C. to about 800° C. Here, the supplying of thefirst reaction gas may include supplying the hydrogen chloride (HCl)with a flow rate greater than 150 times a flow rate of the germane(GeH4).

In at least one exemplary embodiment, the supplying of the firstreaction gas may be performed during a process time of about 1 sec toabout 120 sec, and the supplying of the second reaction gas may beperformed during a process time, of which a ratio relative to that ofthe first reaction gas may be about 0.1 to about 10.

In another feature of the present general inventive concept, a method ofincreasing stress on a channel of a gate structure including in asemiconductor device comprises forming a first trench in the channel,etching the first trench to form a second trench having corners beingsubstantially pointed, the corners including a tip portion extendinglaterally with respect to the channel and beneath the gate structure,and forming a junction region having a lattice constant different from amaterial of the channel to exert a stress on the channel.

In yet another feature of the present general inventive concept, asemiconductor device comprises a trench having corners extendinglaterally with respect to the channel and beneath the gate structure,the corners including a tip portion having a curvature of at most 5 nm,and a junction region having a lattice constant different from amaterial of the channel to maintain the curvature of the tip portion andexert a stress on the channel.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other features and utilities of the present generalinventive concept will become apparent and more readily appreciated fromthe following description of the exemplary embodiments, taken inconjunction with the accompanying drawings of which:

FIGS. 1A through 1I are sectional views illustrating methods offabricating a semiconductor device according to exemplary embodiments ofthe present general inventive concept;

FIGS. 2A and 2B are sectional views illustrating a non-cycling process,which may be performed in methods of fabricating a semiconductor deviceaccording to exemplary embodiments of the present general inventiveconcept;

FIGS. 2C through 2E are graphs of germanium content measured from asemiconductor device fabricated by the method including the non-cyclingprocess;

FIGS. 3A and 3B are sectional views illustrating a cycling process,which may be performed in methods of fabricating a semiconductor deviceaccording to exemplary embodiments of the present general inventiveconcept;

FIGS. 3C through 3E are graphs of germanium content measured from asemiconductor device fabricated by the method including the cyclingprocess;

FIG. 4A is a graph illustrating a relationship between a processcondition and a tip rounding;

FIG. 4B is a graph illustrating a relationship between a processcondition and deformation of a device isolation layer;

FIG. 5A is a block diagram illustrating a memory card including asemiconductor device according to exemplary embodiments of the presentgeneral inventive concept;

FIG. 5B is a block diagram illustrating an information processing systemincluding a semiconductor device according to exemplary embodiments ofthe present general inventive concept; and

FIG. 6 is a flowchart illustrating an exemplary method of fabricating asemiconductor device.

It should be noted that these figures are intended to illustrate thegeneral characteristics of methods, structure and/or materials utilizedin certain exemplary embodiments and to supplement the writtendescription provided below. These drawings are not, however, to scaleand may not precisely reflect the precise structural or performancecharacteristics of any given embodiment, and should not be interpretedas defining or limiting the range of values or properties encompassed byexemplary embodiments. For example, the relative thicknesses andpositioning of molecules, layers, regions and/or structural elements maybe reduced or exaggerated for clarity. The use of similar or identicalreference numbers in the various drawings is intended to indicate thepresence of a similar or identical element or feature.

DETAILED DESCRIPTION OF THE EXEMPLARY EMBODIMENTS

Reference will now be made in detail to the exemplary embodiments of thepresent general inventive concept, examples of which are illustrated inthe accompanying drawings, wherein like reference numerals refer to thelike elements throughout. The exemplary embodiments are described belowin order to explain the present general inventive concept whilereferring to the figures.

It will be understood that when an element is referred to as being“connected” or “coupled” to another element, it can be directlyconnected or coupled to the other element or intervening elements may bepresent. In contrast, when an element is referred to as being “directlyconnected” or “directly coupled” to another element, there are nointervening elements present. Like numbers indicate like elementsthroughout. As used herein the term “and/or” includes any and allcombinations of one or more of the associated listed items. Other wordsused to describe the relationship between elements or layers should beinterpreted in a like fashion (e.g., “between” versus “directlybetween,” “adjacent” versus “directly adjacent,” “on” versus “directlyon”).

It will be understood that, although the terms “first”, “second”, etc.may be used herein to describe various elements, components, regions,layers and/or sections, these elements, components, regions, layersand/or sections should not be limited by these terms. These terms areonly used to distinguish one element, component, region, layer orsection from another element, component, region, layer or section. Thus,a first element, component, region, layer or section discussed belowcould be termed a second element, component, region, layer or sectionwithout departing from the teachings of exemplary embodiments.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein describes particular exemplary embodimentsand is not intended to be limiting of exemplary embodiments. As usedherein, the singular forms “a,” “an” and “the” are intended to includethe plural forms as well, unless the context clearly indicatesotherwise. It will be further understood that the terms “comprises”,“comprising”, “includes” and/or “including,” if used herein, specify thepresence of stated features, integers, steps, operations, elementsand/or components, but do not preclude the presence or addition of oneor more other features, integers, steps, operations, elements,components and/or groups thereof.

Exemplary embodiments of the present general inventive concept aredescribed herein with reference to cross-sectional illustrations thatare schematic illustrations of idealized exemplary embodiments (andintermediate structures) of exemplary embodiments. As such, variationsfrom the shapes of the illustrations as a result, for example, ofmanufacturing techniques and/or tolerances, are to be expected. Thus,exemplary embodiments of the present general inventive concept shouldnot be construed as limited to the particular shapes of regionsillustrated herein but are to include deviations in shapes that result,for example, from manufacturing. For example, an implanted regionillustrated as a rectangle may have rounded or curved features and/or agradient of implant concentration at its edges rather than a binarychange from implanted to non-implanted region. Likewise, a buried regionformed by implantation may result in some implantation in the regionbetween the buried region and the surface through which the implantationtakes place. Thus, the regions illustrated in the figures are schematicin nature and their shapes are not intended to illustrate the actualshape of a region of a device and are not intended to limit the scope ofexemplary embodiments.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which exemplary embodiments of thepresent general inventive concept belong. It will be further understoodthat terms, such as those defined in commonly-used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the relevant art and will not be interpreted in anidealized or overly formal sense unless expressly so defined herein.

FIGS. 1A through 1I are sectional views illustrating methods offabricating a semiconductor device according to exemplary embodiments ofthe present general inventive concept, and FIGS. 1E through 1G areenlarged sectional views of a portion of the semiconductor device shownin FIG. 1D.

Referring to FIG. 1A, a semiconductor substrate 101 may be provided. Thesemiconductor substrate 101 may be a material with a semiconductorproperty (e.g., silicon). For instance, the semiconductor substrate 101may include a silicon wafer with a (100) crystal plane. At least onegate electrode structure 119 may be formed on a surface 101 a of thesemiconductor substrate 101 (operation 610 of FIG. 6). The surface 101 amay have the (100) crystal plane. A gate insulating layer 111 may beformed on the semiconductor substrate 101, and a plurality of gates 113may be formed on the gate insulating layer 111. In some exemplaryembodiments, gate spacers 117 may be formed on sidewalls 113 a of thegates 113. In some exemplary embodiments, the gate insulating layer 111may include at least one of an oxide layer (e.g., SiO2), a nitride layer(e.g., SiN, Si3N4, and SiON), or a high-k dielectric (e.g., HfO2, andZrO2). The gate 113 may include at least one of a doped polysiliconlayer, an undoped polysilicon layer, a metal layer, or any combinationthereof. For instance, the gate 113 of an NMOS transistor may include apolysilicon layer doped with arsenic (As) and/or phosphorus (P), and thegate 113 of a PMOS transistor may include a polysilicon layer doped withboron (B). The gate spacer 117 may be formed of an oxide layer, anitride layer, or any combination thereof. On the gate 113, there mayfurther be a hard mask layer 115, which may be formed of an oxide layer,a nitride layer, or any combination thereof. A portion of thesemiconductor substrate 101, which is located below the gate electrodestructure 119, may serve as a channel 112, i.e., a pathway, to transportone or more carriers.

Referring to FIG. 1B, first trenches 123 may be formed by etchingportions of the semiconductor substrate 101, which are exposed betweenthe gate electrode structures 119 (operation 620 of FIG. 6). In someexemplary embodiments, an isotropic dry etching technique may be used toform the trenches 123 in the semiconductor substrate 101. The isotropicdry etching technique may be performed using an etchant having highreactivity toward silicon of the semiconductor substrate 101, forinstance, a mixture gas plasma of hydrogen bromide (HBr) and chlorine(Cl2), a mixture gas plasma of sulphur hexafluoride (SF6) and chlorine(Cl2), or a mixture gas plasma of hydrogen bromide (HBr), chlorine(Cl2), and sulphur hexafluoride (SF6). In some exemplary embodiments,portions of the semiconductor substrate 101 exposed between the gatespacers 117 may be vertically etched at an initial stage of theisotropic dry etching process, but portions of the semiconductorsubstrate 101 located below the gate spacers 117 may be laterally andvertically etched as the isotropic dry etching process progresses. As aresult, portions of the semiconductor substrate 101 may be undercutbelow the gate electrode structure 119. Accordingly, the first trench123 may include an undercut cavity 123 a that extends laterally beneaththe gate electrode structure 119. In at least one exemplary embodimentthe undercut cavity 123 a may be formed beneath the gate spacer 117 ofthe gate electrode structure 119. The first trench 123 may be formed ofvarious shapes including, but not limited to, an elliptical shape. Inother exemplary embodiments, the formation of the first trench 123 mayinclude forming recess regions 121 using an anisotropic dry etchingprocess and then laterally enlarging the recess regions 121 using theisotropic dry etching process. The anisotropic dry etching process maybe performed using a mixture gas plasma of fluorine (F), carbon (C),oxygen (O) and argon (Ar), for instance, CF4/O2/Ar plasma or CHF3/O2/Arplasma.

Referring to FIG. 10, second trenches 125 may be formed in thesemiconductor substrate 101 (operation 630 of FIG. 6). The formation ofthe second trench 125 may include, for instance, further manipulatingthe first trench 123 using a wet etching process. For example, the firsttrenches 123 may be enlarged to form the second trenches 123.

In at least one exemplary embodiment, a wet etching process may beperformed using at least one etchant including, but not limited to,ammonium hydroxide (NH4OH), tetramethylammonium hydroxide (TMAH;(CH3)4NOH), potassium hydroxide (KOH), sodium hydroxide (NaOH), BTMH(benzoic acid [(thiophen-2-yl)methylene] hydrazide), amine etchant, orany combination thereof. In at least one exemplary embodiment, thesemiconductor substrate 101 includes a single-crystal silicon. In thiscase, a (111) crystal plane has a relatively high density compared withother crystal planes, and therefore, an etching amount of the (111)crystal plane may be saturated during the wet etch process. As a result,after the wet etch process, a surface 125 s of the second trench 125 maymainly consist of inner surfaces with (111) crystal plane, e.g., a firstplane 125 a and a second plane 125 b. In other words, the second trench125 may be formed to have a sigma (Σ) profile. The first plane 125 a andthe second plane 125 b may come in contact with each other in such a waythat they form a corner including a sharp tip 125 t sharply protrudingtoward the channel 112, and extending laterally beneath the gateelectrical structure. In at least one exemplary embodiment, the tip 125t of the second trench 125 extends laterally beneath the spacer 117 andis aligned with the side wall 113 a of the respective gate 113. The tips125 t having the sharp shape increase the stress applied to the channel112, as discussed in greater detail below.

In some exemplary embodiments, the second planes 125 b may come incontact with each other in such a way that they form a tip 125 d at thebottom of the second trench 125. In other exemplary embodiments, a thirdplane 125 c with (100) crystal plane may form the bottom surface of thesecond trench 125. Alternatively, by adjusting a process time in the wetetching process, the second trench 125 may be formed not to have thethird crystal plane 125 c.

Referring to FIG. 1D, a cleaning process may be performed to remove acontaminant, such as a native oxide layer, which may be formed on thesurface 125 s of the second trench 125. In some exemplary embodiments,the surface 125 s of the second trench 125 may be used as a seed layerto grow a subsequent epitaxial layer (identified by a reference numeral150 of FIG. 2H). Since the contaminant e.g., the native oxide layer, maybe removed from the surface 125 s of the second trench 125 during thecleaning process, it may be possible to form a high quality epitaxiallayer. In some exemplary embodiments, the cleaning process may include afirst operation configured to remove the native oxide layer using afirst reaction gas (operation 640 of FIG. 6) and a second operationconfigured to remove other contaminants or an unintended layer using asecond reaction gas (operation 650 of FIG. 6), which may be sequentiallyperformed. Hereinafter, a process of sequentially performing the firstand second operations will be called a cycling process. The cleaningprocess may include performing the cycling process at least one time.The cycling process will be described in more detail with reference toFIGS. 1E through 1G, in which a portion 126 of the surface 125 s of thesecond trench 125 is enlarged.

Referring to FIGS. 1D and 1E, the native oxide layer 180 may be formedon the surface 125 s of the second trench 125. In the case that thesemiconductor substrate 101 is formed of silicon (Si), the native oxidelayer 180 may be a silicon oxide layer (SiOx).

Referring to FIG. 1F, the first reaction gas may be supplied onto thesemiconductor substrate 101 to remove the native oxide layer 180(operation 640 of FIG. 6). The first reaction gas may be a gascontaining germanium. In some exemplary embodiments, the first reactiongas may include germane or germanium tetrahydride (GeH4). The germane(GeH4) may be decomposed into germanium (Ge) and hydrogen (H2), asfollows:GeH4→Ge+2H2.  (Reaction Formula 1)

Then, the germanium (Ge) decomposed from germane (GeH4) may be reactedwith silicon oxide (SiOx) of the native oxide layer 180 to form avolatile germanium oxide (GeO), as follows:xGe+SiOx→xGeO↑+Si.  (Reaction Formula 2)

In some exemplary embodiments, the native oxide layer 180 on the surface125 s of the second trench 125 may be removed through various reactionswith the germane gas (GeH4) described in the following reaction formulas3 to 6.GeH4+(2/x)SiOx→H2O↑+H2↑+GeO↑+(2/x)Si  (Reaction Formula 3)(x−1)GeH4+SiOx→(x−1)GeO↑T+SiO↑+2(x−1)H2↑  (Reaction Formula 4)xGeH4+SiOx→xGeO↑+2xH2↑+Si  (Reaction Formula 5)xGeH4+SiOx→xGeO↑+SiH4  (Reaction Formula 6)

Since, as shown in the reaction formulas 1 to 6, germanium (Ge)decomposed from germane gas (GeH4) may be reacted with silicon oxide(SiOx) to form a volatile germanium oxide (GeO), the native oxide layer180 may be removed.

In addition to the removal of the native oxide layer 180, the supplyingof germane gas (GeH4) may result in a germanium layer 190 deposited onthe surface 125 s, as described by the following reaction formula 7.xGeH4+2SiOx→xGe+2xH2O↑+2Si  (Reaction Formula 7)

In some exemplary embodiments, the first reaction gas may furtherhydrogen chloride (HCl) serving as an etchant to remove the germaniumlayer 190. The hydrogen chloride (HCl) may be reacted with the germaniumlayer 190 to form gaseous germanium chloride (GeClx), as described bythe following reaction formula 8. Therefore, the germanium layer 190 maybe removed.Ge(s)+2HCl(g)→GeCl2(g)+H2(g)  (Reaction Formula 8)

As described above, the first reaction gas may include the germane(GeH4) supplied as an etchant to remove the native oxide layer 180 andthe hydrogen chloride (HCl) supplied as an etchant to remove thegermanium layer 190 and/or as a controlling gas to suppress a depositionof the germanium layer 190. The first reaction gas may further include ahydrogen gas (H2), which may be used to control a concentration ofgermanium (Ge) and/or as a carrier gas of the hydrogen chloride (HCl).

In some exemplary embodiments, the first operation supplying the firstreaction gas containing a mixture gas of germane (GeH4), hydrogenchloride (HCl), and hydrogen (H2) onto the semiconductor substrate 101may be performed under a pressure of about 1 Torr to about 100 Torr at atemperature of about 500° C. to about 800° C. (more particularly, about500° C. to about 700° C. or about 650° C. to about 700° C.) for about 1sec to about 120 sec. During the first operation, the hydrogen (H2) maybe supplied with a flow rate of about 30 slm to about 50 slm, thehydrogen chloride (HCl) may be supplied with a flow rate of about 150sccm or more, and the germane (GeH4) may be supplied with a flow rate ofabout 0.75 sccm or more. A ratio in flow rate of the hydrogen chloride(HCl) to the germane (GeH4) may be 150 or more, for instance, 200. Apartial pressure of the germane (GeH4) may be controlled about 0.3 mTorror less, and a partial pressure of the hydrogen chloride (HCl) may begreater than that of the germane (GeH4). For instance, a ratio inpartial pressure of the hydrogen chloride (HCl) to the germane (GeH4)may be about 150 or more.

In at least one exemplary embodiment, the first operation may beperformed, for about 60 sec, under a process condition described in thefollowing table 1, where the first reaction gas may be supplied with atotal flow rate of 40150.75 sccm and a ratio in flow rate of thehydrogen chloride (HCl) to the germane (GeH4) may be controlled to beabout 200.

TABLE 1 Atomic Flow Rate Percentage Partial Pressure PressureTemperature (sccm) (atomic %) (mTorr) (Torr) (° C.) H₂ 40,000 0.996259962.45 10 680 HCl 150 0.00374 37.36 GeH₄ 0.75 1.9E−0.5 0.19

By the first operation, the native oxide layer 180 may be removed fromthe surface 125 s. As will be described with reference to FIGS. 2Athrough 2E, when the cleaning process is performed in a non-cyclingmanner (i.e., only with the first operation), some germanium atoms maybe un-etched or produced from the decomposition of the germane (GeH4) todetectably remain on the surface 125 s of the second trench 125. Inaddition to the presence of empirically detectable germanium atoms,performing only the first operation may result in a deformation of thesecond trench 125 with the sigma profile. For example, the tips 125 tand 125 d thereof may be deformed to have rounded shapes, as opposed tothe sharp tips 125 t illustrated in FIGS. 1C, 1D, 1H and 1I. The secondoperation of supplying the second reaction gas may contribute topreserve sharp shapes of the tips 125 t and 125 d, and may assist ineffectively removing the extra germanium layer 190. Accordingly,preserving the sharp shapes of the tips 125 t and 125 d may provide animproved junction 150 that more effectively provides a stress to thechannel 112.

Referring to FIGS. 1D and 1G, after the first operation of removing ofthe native oxide layer 180, the second reaction gas may be supplied ontothe semiconductor substrate 101 to remove the extra germanium layer 190(operation 650 of FIG. 6). The second reaction gas may include ahydrogen chloride (HCl) gas. In addition, the second reaction gas mayfurther include a hydrogen (H2) gas as a carrier gas of the hydrogenchloride (HCl) gas. In the case that a mixture gas of hydrogen chloride(HCl) and hydrogen (H2) is supplied onto the semiconductor substrate101, as described with reference to the above reaction formula 8, theextra germanium layer 190 may be etched to form an etched germaniumlayer 192 and removed from the surface 125 s at a final stage of thecleaning process. In addition, the surface 125 s of silicon may bereacted with the hydrogen chloride (HCl) gas to form an etched portion170 as described with reference to the following reaction formula 9. Insome exemplary embodiments, the silicon may be etched to form the etchedportion 170 on the surface 125 s. In some exemplary embodiment, theetched portion 170 may be formed by a reaction between the hydrogenchloride (HCl) gas and a silicon-germanium (SiGe) layer on the surface125 s, which may be formed from a reaction of Ge and Si.Si(s)+2HCl(g)→SiCl2(g)+H2(g)  (Reaction Formula 9)

In some exemplary embodiments, ways of adjusting the flow rate of thehydrogen chloride (HCl) gas and/or an operation time of the secondoperation may be used to suppress or prevent the etched portion 170 fromoccurring. In at least one exemplary embodiment, the second operationmay be performed using the substantially same environmental condition asthe first operation. For instance, the first and second operations maybe sequentially performed using the process condition given by the abovetable 1, under the same pressure of and temperature conditions, whichmay be selected in a range of about 1 Torr to about 100 Torr and about500° C. to about 800° C. (more particularly, about 10 Torr and about680° C.).

In other exemplary embodiments, the second operation may be performedusing an environmental condition, which is similar to the firstoperation but differs from the first operation in that the temperaturemay be in a range of about 700° C. to about 800° C. and/or a ratio inoperation time of the first operation to the second operation may be setto be in about 0.1 to about 10.

In still other exemplary embodiments, the first operation may beperformed at a temperature of about 500° C. to about 700° C. or about650° C. to about 700° C., while other process conditions thereof may bethe same as the aforementioned conditions. The second operation may beperformed at a temperature range of about 700° C. to about 800° C.and/or with a ratio in operation time of the first operation to thesecond operation that is set to be in about 0.1 to about 10.

According to exemplary embodiments of the present general inventiveconcept, the performing the cycling process at least one time may makeit possible to preserve the sharp profile of the second trench 125 andto effectively remove the native oxide layer 180 and the extra germaniumlayer 190.

In at least one exemplary embodiment, the cleaning process may includethe cycling process performed at a temperature of 700° C. or more, andanother cycling process or the first operation may be performed at atemperature of 700° C. or less. Even when the cleaning process includesonly the first operation performed at a temperature of 700° C. or less,if the ratio in flow rate of hydrogen chloride (HCl) to germane (GeH4)is relatively high (e.g., greater than about 150), the native oxidelayer 180 and the extra germanium layer 190 may be effectively removed.

As shown in FIGS. 1H and 1I, a material with a lattice constantdifferent from silicon (Si) may be epitaxially grown from the secondtrench 125 (operation 660 of FIG. 6). In some exemplary embodiments, acompressive stress caused by the difference in lattice constant may beexerted on the channel 112, as shown in a semiconductor device 10 ofFIG. 1H. In other exemplary embodiments, a tensile stress caused by thedifference in lattice constant may be exerted on the channel 112, asshown in a semiconductor device 20 of FIG. 1I. At least one of thesemiconductor devices 10 and 20 may include at least one memory elementand moreover, may be used to realize a memory card, a mobile device, ora computer.

In more detail, referring to FIG. 1H, the second trench 125 may befilled with silicon-germanium (SiGe) to form a junction region 150. Theformation of the junction region 150 may include epitaxially growing asilicon-germanium layer from the second trench 125 and then doping thesilicon-germanium layer with boron (B) atoms. Alternatively, thejunction region 150 may be formed by epitaxially growing a boron-dopedsilicon-germanium layer. The junction region 150 of silicon-germanium(SiGe) may have a greater lattice constant than the channel 112 ofsilicon (Si), the junction region 150 may exert a compressive stress(depicted by a solid arrow line) on the channel 112. As a result, PMOStransistors of the semiconductor device 10 may have increased mobilityof majority carriers (i.e., holes).

According to exemplary embodiments of the present general inventiveconcept, the cycling process may make it possible to effectively removethe native oxide layer and the extra germanium layer from the surface125 s of the second trench 125, and thus, a high quality epitaxial layer(i.e., the junction region 150) may be grown fast compared with theabsence of the cycling process. In addition, since it is possible topreserve the sharp shape of the second trench 125, stress may beeffectively applied to the channel 112. Exemplary embodiments describedwith reference to FIG. 1I may have the above technical features. In atleast one exemplary embodiment, a silicide layer 160 may be additionallyformed on the junction region 150 to reduce a contact resistance betweenthe junction region 150 and a plug (not shown) coupled thereto. Thesilicide layer 160 may be formed between adjacent gate electrodestructures 119. Each silicide layer 160 may further include opposingends, each which are coupled to a spacer 117 of the respective gateelectrode structure 119.

Referring to FIG. 1I, a junction region 152 may be formed by filling thesecond trench 125 with a silicon-carbide (SiC) layer. The formation ofthe junction region 152 may include epitaxially growing asilicon-carbide layer from the second trench 125 and then doping thesilicon-carbide layer with phosphorus (P) or arsenic (As) atoms.Alternatively, the junction region 152 may be formed by epitaxiallygrowing a phosphorus (P) or arsenic (As)-doped silicon-carbide layer.The junction region 152 of silicon-carbide (SiC) may have a smallerlattice constant than the channel 112 of silicon (Si), the junctionregion 152 may exert a tensile stress (depicted by a dotted arrow line)on the channel 112. As a result, NMOS transistors of the semiconductordevice 20 may have increased mobility of majority carriers (i.e.,electrons). In some exemplary embodiments, the silicide layer 160 may beadditionally formed on the junction region 152 to reduce a contactresistance between the junction region 152 and a plug coupled thereto.

[Non-Cycling Process]

FIGS. 2A and 2B are sectional views illustrating a non-cycling process,which may be performed in methods of fabricating a semiconductor deviceaccording to exemplary embodiments of the present general inventiveconcept. FIGS. 2C through 2E are graphs of germanium content measuredfrom a semiconductor device fabricated by the method including thenon-cycling process.

Referring to FIG. 2A, as described with reference to FIG. 1F, in thecase that only the first operation is performed, the tips 125 t and 125d of the second trench 125 may result in a rounded shape without anysharp corner, due to migration of silicon atoms in the semiconductorsubstrate 101. The rounded tip 125 t at both sides of the second trench125 may fail in effectively applying stress to the channel 112, comparedwith the case having the sharp shape. Moreover, in the case that the tip125 d at a bottom of the second trench 125 is rounded, the second trench125 may expose planes having more defects than the (111) crystal plane.Consequently, an epitaxial growth rate of SiGe or SiC may become slow.These difficulties may occur even in the case that the bottom of thesecond trench 125 is the (100) crystal plane like the third plane 125 cshown in FIG. 10.

Referring to FIG. 2B, in addition to the rounding of the second trench125, the tip 125 t of the second trench 125 may be excessively deformedaround a device isolation layer 103. In this case, the epitaxial layer(i.e., the junction region 150 or 152 of SiGe or SiC, respectively) maybe improperly grown from the second trench 125. For example, a topsurface 151 s of the epitaxial layer may be lowered, thereby resultingin a slanted top surface 151 s extending between isolation layer and anadjacent gate electrode structure 119. The lowering of the top surface151 s of the epitaxial layer may lead to technical difficultiesassociated to the connection between the plug and/or the silicide layer160, and the epitaxial layer (i.e., the junction region 150 or 152 ofSiGe or SiC). The second lattice plane 125 b adjacent to the deviceisolation layer 103 may be deformed or rounded as depicted by thereference numeral 128. In this case, due to the presence of the roundedportion 128, the epitaxial layer of SiGe or SiC may be grown with adecreased growth rate, and this may lead to an additional lowering ofthe top surface 151 s of the junction region 150 or 152.

If the cleaning process is performed using only the first operation,unintentional germanium atoms may remain on the surface 125 s of thesecond trench 125, in addition to the rounding of the second trench 125and/or the deformation of the tip 125 t. For instance, as shown in FIGS.2C through 2E, germanium atoms may be empirically detected from severalregions of the second trench 125. FIGS. 2C through 2E show atomicpercentages of germanium, which were measured from regions correspondingto the first plane 125 a, the second plane 125 b, and the tip 125 d,respectively, using an energy dispersive X-ray (EDX) spectroscopy.

Even when the cleaning process includes only the first operationperformed at a temperature of 700° C. or less, according to otherexemplary embodiments, it may be possible to effectively remove theextra germanium layer 190, to preserve the sharp shapes of the tips 125t and 125 d, as illustrated in FIGS. 1C, 1D, 1H and 1I, and to suppressand/or prevent the deformation of the tip 125 t and the rounding of thesecond lattice plane 125 b, as will be described in the following.

[Cycling Process]

FIGS. 3A and 3B are sectional views illustrating a cycling process,which may be performed in methods of fabricating a semiconductor deviceaccording to exemplary embodiments of the present general inventiveconcept. FIGS. 3C through 3E are graphs of germanium content measuredfrom a semiconductor device fabricated by the method including thecycling process.

Referring to FIG. 3A, the cycling process may be performed on thesemiconductor substrate 101 provided with the second trench 125 at leastone time. In this case, as illustrated in FIGS. 3C through 3E, germaniumatoms may be effectively removed from the surface 125 s of the secondtrench 125 by performing the cycling process at least one time, whereFIGS. 3C through 3E show atomic percentages of germanium, which weremeasured from regions corresponding to the first plane 125 a, the secondplane 125 b, and the tip 125 d, respectively, using an energy dispersiveX-ray (EDX) spectroscopy. Meanwhile, it should be noted that thepresence of carbon and oxygen, depicted in the graphs of FIGS. 3Cthrough 3E, are originated from materials associated with preparation ofEDX samples and are irrelevant to exemplary embodiments of the presentgeneral inventive concept.

According to exemplary embodiments of the present general inventiveconcept, the tips 125 t and 125 d of the second trench 125 may bemaintained in the sharp shape. For instance, as shown in FIG. 4A, thecurvature or rounding of the tip 125 t may be very small, i.e., about 4nm. FIG. 4A is a graph illustrating a relationship between a processcondition and a tip rounding. Referring to FIG. 4A in conjunction withFIG. 3A, when the first operation supplying the first reaction gas isperformed at 650° C. to 700° C. or when the first and second operationssupplying the first and second reaction gases, respectively, aresequentially performed, the curvature of the tip 125 t was about 5 nm orless. From FIG. 4A, it can be said that the process temperature of 680°C. or less makes it possible for the tip 125 t to have a curvature ofabout 4 nm or less or a sharp shape. It may be similar in effect to thetip 125 d. Since the tips 125 t and 125 d can be maintained in the sharpshape, stress can be effectively applied to the channel 112 and theepitaxial layer of SiGe or SiC can be properly grown.

According to exemplary embodiments of the present general inventiveconcept, as shown in FIG. 3B, the tip 125 t may be formed without anyserious deformation or collapse thereof, even near the device isolationlayer 103. In other words, it may be possible to suppress a surface 151sa of the junction region 150 or 152 from being lowered and/or slanted.Even in the case that the tip 125 t is deformed or collapsed, suchdeformation may be remarkably reduced compared with the exemplaryembodiments described with reference to FIG. 2B, and thus, it may bepossible to suppress a surface 151 sa of the junction region 150 or 152from being excessively lowered and/or slanted.

An STI collapse, in which the second plane 125 b adjacent to the deviceisolation layer 103 is collapsed and rounded as depicted by thereference numeral 127, may occur regardless of, or in conjunction with,the deformation of the tip 125 t. The term “STI collapse” may refer to acollapse or deformation of the tip 125 t of the second trench 125adjacent to the device isolation layer 103 and/or a collapse ordeformation of the sigma profile. Even in the case that the second plane125 b is rounded, the collapse height H may be about 8 nm or less, asshown in FIG. 4B.

FIG. 4B is a graph illustrating a relationship between a processcondition and deformation of a device isolation layer. As shown in FIG.4B, the collapse height H may be controlled down to less than about 5 nmby adjusting the process condition, such as the flow rate of germane(GeH4), the process time, and/or the process temperature. As mentionedabove, the STI collapse may not lead to a remarkable change of thegrowth rate of the epitaxial layer of SiGe or SiC.

FIG. 5A is a block diagram illustrating a memory card including asemiconductor device according to exemplary embodiments of the presentgeneral inventive concept. FIG. 5B is a block diagram illustrating aninformation processing system including a semiconductor device accordingto exemplary embodiments of the present general inventive concept.

Referring to FIG. 5A, a memory card 1200 may be realized using a memorydevice 1210 including at least one of the semiconductor devices 10 and20 according to exemplary embodiments of the present general inventiveconcept. In some exemplary embodiments, the memory card 1200 may includea memory controller 1220 controlling general data exchanges between ahost and the memory device 1210. A static random access memory (SRAM)1221 may be used as an operating memory of a processing unit 1222. Ahost interface 1223 may include a data exchange protocol of a hostconnected to a memory card 1200. An error correction block 1224 maydetect and correct errors included in data read from a multi-bit memorydevice 1210. A memory interface 1225 may interface with the memorydevice 1210. A processing unit 1222 may perform general controloperations to exchange data of the memory controller 1220.

Referring to FIG. 5B, an information processing system 1300 may berealized using a memory system 1310 including at least one of thesemiconductor devices 10 and 20 according to exemplary embodiments ofthe present general inventive concept. For instance, the informationprocessing system 1300 may be a mobile device and/or a desktop computer.In some exemplary embodiments, the information processing system 1300may further include a modem 1320, a central processing unit (CPU) 1330,a RAM 1340, and a user interface 1350, which are electrically connectedto a system bus 1360, in addition to the memory system 1310. The memorysystem 1310 may include a memory device 1311 and a memory controller1312. In some exemplary embodiments, the memory system 1310 may beconfigured substantially identical to the memory system described withrespect to FIG. 5A. Data processed by the CPU 1330 and/or input from theoutside may be stored in the memory system 1310. In some exemplaryembodiments, the memory system 1310 may be used as a portion of a solidstate drive (SSD), and in this case, the information processing system1300 may stably and reliably store a large amount of data in the memorysystem 1310. Although not illustrated, it is apparent to those skilledin the art that, for example, an application chipset, a camera imagesensor, a camera image signal processor (ISP), an input/output device,or the like may further be included in the information processing system1300 according to the present general inventive concept.

According to exemplary embodiments of the present general inventiveconcept, a native oxide layer can be removed from a trench surface usinga reaction gas containing germanium, and a germanium layer, which may beunintentionally deposited on the trench surface, can be removed by acycling process using a reaction gas capable of etching germanium. Inother words, it is possible to effectively remove elements and/orfactors providing a negative effect on a growth rate of an epitaxiallayer. In addition, it is possible to sharply maintain a sigma profileof the trench, and therefore, stress can be effectively applied to achannel region of a transistor. Accordingly, a semiconductor device thatprovides increased carrier mobility may be achieved.

Furthermore, according to exemplary embodiments of the present generalinventive concept, it is possible to suppress and/or prevent the trenchfrom being excessively collapsed and/or deformed. As a result, it ispossible to realize a semiconductor device with improved electricalproperties.

Although a few exemplary embodiments of the present general inventiveconcept have been shown and described, it will be appreciated by thoseskilled in the art that changes may be made in these exemplaryembodiments without departing from the principles and spirit of thegeneral inventive concept, the scope of which is defined in the appendedclaims and their equivalents.

What is claimed is:
 1. A semiconductor device comprising: a semiconductor substrate having a major axis extending horizontally; a first gate structure and a second gate structure disposed on the semiconductor substrate; a shallow trench isolation layer disposed in the semiconductor substrate; a first epitaxial layer disposed in the semiconductor substrate and between the first gate structure and the second gate structure, the first epitaxial layer including a first corner, a second corner and a third corner, the first corner protruding toward a first channel region under the first gate structure, the second corner protruding toward a second channel region under the second gate structure, the third corner protruding downwardly into the substrate; and a second epitaxial layer disposed in the semiconductor substrate and between the second gate structure and the shallow trench isolation layer, the second epitaxial layer including a fourth corner and a fifth corner, the fourth corner protruding toward the second channel region under the second gate structure, the fifth corner protruding downwardly into the substrate, wherein at least a portion of a top surface of the second epitaxial layer is slanted with respect to the major axis, and wherein the portion of the top surface of the second epitaxial layer that is slanted begins extending downward toward the shallow trench isolation layer at an interface of the second epitaxial layer with the second gate structure.
 2. The semiconductor device of claim 1, wherein a first end of the top surface of the second epitaxial layer is lowered as compared to a second end of the top surface of the second epitaxial layer.
 3. The semiconductor device of claim 2, wherein the first end of the top surface of the second epitaxial layer contacts the shallow trench isolation layer, and wherein the first end of the top surface of the second epitaxial layer is disposed lower than a top surface of the shallow trench isolation layer.
 4. The semiconductor device of claim 1, wherein a silicide layer is disposed on the top surface of the second epitaxial layer.
 5. The semiconductor device of claim 1, wherein a spacer of the second gate structure overlaps at least a portion of the top surface of the second epitaxial layer, and wherein a silicide layer is disposed on the top surface of the second epitaxial layer, and the spacer of the second gate structure contacts the silicide layer.
 6. The semiconductor device of claim 1, wherein the top surface of the first epitaxial layer is coplanar with a top surface of the semiconductor substrate.
 7. The semiconductor device of claim 1, wherein a top surface of the first epitaxial layer extends substantially parallel with respect to the major axis.
 8. The semiconductor device of claim 1, wherein the first and second gate structures respectively include a gate electrode.
 9. The semiconductor device of claim 1, wherein the first and second gate structures respectively include a gate insulating layer, a gate electrode, and a gate capping pattern.
 10. The semiconductor device of claim 1, wherein the second gate structure comprises a spacer, wherein the portion of the top surface of the second epitaxial layer that is slanted extends from a contact area between the second epitaxial layer and the spacer of the second gate structure downward toward the shallow trench isolation layer, wherein the top surface of the second epitaxial layer comprises a first surface, and wherein the fifth corner protruding downwardly into the substrate is defined by second and third surfaces of the second epitaxial layer that are slanted with respect to the major axis.
 11. The semiconductor device of claim 1, wherein the portion of the top surface of the second epitaxial layer that is slanted is substantially flat in a plane that is inclined with respect to the major axis.
 12. The semiconductor device of claim 1, wherein the portion of the top surface of the second epitaxial layer that is slanted comprises a single downwardly-sloped surface that contacts the second gate structure and the shallow trench isolation layer.
 13. The semiconductor device of claim 1, wherein the interface at which the portion of the top surface of the second epitaxial layer that is slanted begins extending downward toward the shallow trench isolation layer is overlapped by the second gate structure.
 14. A semiconductor device comprising: a semiconductor substrate having a major axis extending horizontally; a first gate structure and a second gate structure disposed on the semiconductor substrate; a shallow trench isolation layer disposed in the semiconductor substrate; a first epitaxial layer disposed in the semiconductor substrate and between the first gate structure and the second gate structure, the first epitaxial layer including a first corner, a second corner and a third corner, the first corner protruding toward a first channel region under the first gate structure, the second corner protruding toward a second channel region under the second gate structure, the third corner protruding downwardly into the substrate; and a second epitaxial layer disposed in the semiconductor substrate and between the second gate structure and the shallow trench isolation layer, the second epitaxial layer including a fourth corner and a fifth corner, the fourth corner protruding toward the second channel region under the second gate structure, the fifth corner protruding downwardly into the substrate, wherein the first epitaxial layer has a substantially symmetrical cross-sectional profile with respect to an imaginary vertical line crossing the third corner while the second epitaxial layer has a non-symmetrical cross-sectional profile with respect to an imaginary vertical line crossing the fifth corner, and wherein a slanted portion of a top surface of the second epitaxial layer begins extending downward toward the shallow trench isolation layer at an interface of the second epitaxial layer with the second gate structure.
 15. The semiconductor device of claim 14, further comprising a third epitaxial layer disposed adjacent to the first gate structure, and the third epitaxial layer has a substantially symmetrical cross-sectional profile.
 16. The semiconductor device of claim 14, further comprising a third epitaxial layer disposed adjacent to the first gate structure, and the third epitaxial layer has a same cross-sectional profile with the cross-sectional profile of the first epitaxial layer.
 17. The semiconductor device of claim 14, wherein the first and second gate structures respectively include a gate electrode.
 18. The semiconductor device of claim 14, wherein the first and second gate structures respectively include a gate insulating layer, a gate electrode, and a gate capping pattern.
 19. A semiconductor device comprising: a semiconductor substrate having a major axis extending horizontally; a gate structure disposed on the semiconductor substrate; a shallow trench isolation layer disposed in the semiconductor substrate; and an epitaxial layer disposed in the semiconductor substrate and between the gate structure and the shallow trench isolation layer, the epitaxial layer including a first corner and a second corner, the first corner protruding toward a channel region under the gate structure, the second corner protruding downwardly into the substrate, wherein at least a portion of a top surface of the epitaxial layer is slanted with respect to the major axis and an end portion of the slanted top surface contacts the shallow trench isolation layer, and wherein the portion of the top surface of the epitaxial layer that is slanted begins extending downward toward the shallow trench isolation layer at an interface of the epitaxial layer with the gate structure.
 20. The semiconductor device of claim 19, wherein the gate structure includes a gate electrode.
 21. The semiconductor device of claim 19, wherein the gate structure includes a gate insulating layer, a gate electrode, and a gate capping pattern. 